WO2023071336A1 - Nitride/graphitized carbon nanosheet-coated ternary positive electrode material and preparation method therefor - Google Patents

Nitride/graphitized carbon nanosheet-coated ternary positive electrode material and preparation method therefor Download PDF

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WO2023071336A1
WO2023071336A1 PCT/CN2022/108630 CN2022108630W WO2023071336A1 WO 2023071336 A1 WO2023071336 A1 WO 2023071336A1 CN 2022108630 W CN2022108630 W CN 2022108630W WO 2023071336 A1 WO2023071336 A1 WO 2023071336A1
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Prior art keywords
nitride
positive electrode
electrode material
graphitized carbon
ternary positive
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PCT/CN2022/108630
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French (fr)
Chinese (zh)
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许开华
何锐
丁卫丰
张云河
张翔
张坤
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格林美股份有限公司
格林美（湖北）能源材料有限公司
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Priority to EP22885236.4A priority Critical patent/EP4322252A1/en
Priority to JP2023565576A priority patent/JP2024513536A/en
Priority to KR1020237036967A priority patent/KR20230156430A/en
Publication of WO2023071336A1 publication Critical patent/WO2023071336A1/en
Priority to US18/495,730 priority patent/US20240097116A1/en

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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Definitions

  • the invention relates to the technical field of lithium batteries, in particular to a nitride/graphitized carbon nanosheet-coated ternary positive electrode material and a preparation method thereof.
  • lithium-ion batteries are widely used in portable consumer electronics devices due to their advantages such as high working voltage, high energy density, high Coulombic efficiency, no memory effect, long cycle life and environmental friendliness. , new energy vehicles and energy storage grids and other fields.
  • the cathode material of a lithium-ion battery determines the comprehensive performance of the battery.
  • Ni-O bond energy is weak and the stability of the crystal structure becomes poor, especially during the charging and discharging process. Oxidation-reduction reactions occur between the highly active interface and the electrolyte to form an inactive rock-salt phase structure, which causes the electrolyte to decompose and release a large amount of heat at the same time, resulting in a series of problems such as cell inflation, safety performance degradation, discharge capacity decay, and cycle stability deterioration. .
  • one of the main technical means to solve this problem is coating.
  • the coating agent can not only effectively avoid the direct contact between the highly active positive electrode interface and the electrolyte, alleviate the occurrence of side reactions, but also act as a fast ion conductor to facilitate the diffusion of lithium ions.
  • the transmission provides a good channel, which in turn improves the magnification performance.
  • the coating agent mainly includes oxides, such as Al 2 O 3 , TiO 2 , ZrO 2 , B 2 O 3 , SiO 2 , etc.
  • oxides such as Al 2 O 3 , TiO 2 , ZrO 2 , B 2 O 3 , SiO 2 , etc.
  • the oxide coating agent can improve the above interface stability problems, most of the oxides Belonging to semiconductors, the electronic conductivity is low and cannot meet the requirements of high current charging and discharging.
  • nitrides have better chemical corrosion resistance, more excellent electronic conductivity and thermal stability, and as coating agents, they can maximize the electrical properties of ternary materials.
  • the gas phase deposition coating method is adopted, and the gas phase reaction process is complicated, and it is not easy to produce on a large scale.
  • the ternary cathode material to be coated, titanium source, and nitrogen-containing compound are mixed and sintered in one step to prepare the titanium nitride-coated ternary cathode material, although the method is simple and convenient for industrial production , but in the preparation process, the reducing gas of the nitrogen-containing compound may directly react with the ternary material, thereby destroying the lattice structure of the ternary positive electrode main material and affecting the electrical performance of the material.
  • a first aspect of the present invention provides a nitride/graphitized carbon nanosheet coated ternary positive electrode material, including a ternary positive electrode material substrate and a coating layer, the coating layer is composed of nitride and graphitized carbon, and graphitized The carbon is formed in situ during the coating of the nitride.
  • a second aspect of the present invention provides a method for preparing a nitride/graphitized carbon nanosheet-coated ternary positive electrode material, comprising the following steps:
  • the intermediate product is uniformly mixed with the carbon and nitrogen-containing compound, sintered, pulverized, sieved and iron removed to obtain a nitride/graphitized carbon nanosheet-coated ternary positive electrode material.
  • a graphitized carbon layer structure is generated in situ.
  • the carbon layer generated in situ is more tightly connected to the matrix material, and the conductive network is denser. , so as to maximize the rate performance of the material; the ternary cathode material has excellent rate performance and cycle stability, and its preparation method has a simple process flow and is easy to realize industrial production.
  • a first aspect of the present invention provides a nitride/graphitized carbon nanosheet coated ternary positive electrode material, including a ternary positive electrode material substrate and a coating layer, the coating layer is composed of nitride and graphitized carbon, and graphitized The carbon is formed in situ during the coating of the nitride.
  • graphitized carbon materials Compared with amorphous carbon, graphitized carbon materials have better conductivity and are more conducive to improving the rate performance.
  • the nitride is one or more of aluminum nitride, silicon nitride, titanium nitride, zirconium nitride, tantalum nitride, and niobium nitride.
  • the thickness of the coating layer is 1 to 100 nm.
  • a second aspect of the present invention provides a method for preparing a nitride/graphitized carbon nanosheet-coated ternary positive electrode material, comprising the following steps:
  • the transition metal nitride is produced by reacting the nitrogen element in the carbon-nitrogen-containing compound with the transition metal oxide coated on the surface of the intermediate product in a high-temperature environment, and at the same time, the carbon element is generated in situ under the catalytic graphitization of the transition metal Graphitized carbon nanosheets eventually form a nitride/graphitized carbon nanosheets-coated ternary cathode material.
  • the step of providing the matrix of the ternary positive electrode material is specifically: mixing the precursor of the ternary positive electrode material and the lithium source evenly, and then calcining, pulverizing, and sieving to obtain the matrix of the ternary positive electrode material.
  • the precursor of the ternary positive electrode material is one or more of oxides, hydroxides, and oxyhydroxides of nickel-cobalt-manganese or nickel-cobalt-aluminum; the lithium source is lithium carbonate, lithium oxide, and lithium hydroxide.
  • the molar ratio of the precursor of the ternary cathode material to the lithium source is 1:1 ⁇ 1.15; the precursor of the ternary cathode material and the lithium source are mixed evenly by the high mixer; the speed of the high mixer is 100 ⁇ 1500rpm, further 1000rpm, the mixing treatment time is 0.5 ⁇ 5h, further 1h; the calcination is carried out under the oxygen atmosphere, the volume concentration of the oxygen atmosphere is ⁇ 99%, the calcination temperature is 500 ⁇ 1200°C, further 650 ⁇ 850 °C, further 750 °C; calcination time 5-24h, further 10-14h, further 12h.
  • dopants are also added to improve the structural stability of the cathode material.
  • the dopant can be zirconium dioxide, aluminum trioxide, titanium dioxide, magnesium oxide, etc., which is not limited in the present invention.
  • the molar ratio of the dopant to the precursor of the ternary cathode material is 0.0001 ⁇ 0.1:1.
  • the mass ratio of the coating element to the matrix of the ternary positive electrode material is 0.0001-0.005:1, further 0.0004-0.003:1, and further 0.0008-0.001:1.
  • the steps of wet coating are specifically:
  • the compound containing a coating element is an alkoxide containing a coating element.
  • the compound containing coating elements is aluminum triethoxide, ethyl orthosilicate, tetrabutyl titanate, titanium isopropoxide, zirconium isopropoxide, tantalum pentaethoxide, pentaethoxide
  • One or more of niobium ethoxide; the first solvent and the second solvent are one or more of water, methanol, ethanol, isopropanol, and ethylene glycol.
  • the dosage ratio of the ternary cathode material matrix to the solvent is 1-20g: 100ml, further 10-20g: 100ml; in solution II, the dosage ratio of the compound containing the coating element to the solvent is 0.01- 10g: 100ml, further 0.04-1g: 100ml, further 0.1-0.6g: 100ml, further 0.2g: 100ml.
  • the temperature of the heat preservation reaction is 30-80°C, further 60°C, the time of the heat preservation reaction is 0.5-5h, further 1-2h; the temperature of the drying is 80-120°C, and the drying time is 5-20h.
  • the carbon-nitrogen-containing compound is one or more of amino acids, melamine, and urea.
  • the mass ratio of carbon and nitrogen-containing compounds to intermediate products is 5-20:100. If the mass ratio is too high, it will cause too much surface coating (nitride and graphitized carbon), which will affect the capacity of the material; if it is too low, the There are few coating layers, and the coating effect cannot be achieved; the further ratio is 6-17:100, and the further ratio is 10:100; the carbon-nitrogen-containing compound and the intermediate product are mixed evenly by a high-speed mixer, and the speed of the high-speed mixer is 1000 ⁇ 4000rpm, further 2000rpm, mixing treatment time is 1-8h, further 2h; sintering is carried out under the protection of inert gas (such as argon or nitrogen, etc.), the sintering temperature is 500-1000°C, further 800°C, the sintering time 3 ⁇ 12h, further 6h.
  • inert gas such as argon or nitrogen, etc.
  • Button battery test Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ⁇ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity 210mAh/g, 1C discharge capacity 199mAh/g, 50-cycle cycle capacity retention rate 98.6%.
  • Button battery test Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ⁇ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity of 208mAh/g, 1C discharge capacity of 194mAh/g, 50-cycle cycle capacity retention rate of 93.7%.
  • Button battery test Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ⁇ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity 209mAh/g, 1C discharge capacity 196mAh/g, 50-cycle cycle capacity retention rate 97.9%.
  • Button battery test Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ⁇ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity 207mAh/g, 1C discharge capacity 193mAh/g, 50-cycle cycle capacity retention rate 97.4%.
  • Button battery test Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ⁇ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity of 198mAh/g, 1C discharge capacity of 176mAh/g, 50-cycle cycle capacity retention rate of 97.5%.
  • Button battery test Mix the obtained nitride-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, mix evenly with NMP as a solvent, and coat on an aluminum foil Firstly, make 2032 button cells for electrochemical performance test, the test voltage range is 2.8 ⁇ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity 206mAh/g, 1C discharge capacity 190mAh/g, 50-cycle cycle capacity retention rate 97.0%.
  • the preparation method has a simple technological process, a pure solid phase reaction process, convenient control of conditions, and easy large-scale industrial production;
  • the entire coating process is divided into wet pre-coating and subsequent high-temperature nitriding steps.
  • the pre-coating process not only provides a precursor for subsequent nitriding, but also protects the ternary cathode substrate The material is protected from subsequent carbon and nitrogen-containing reducing gas damage;

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Abstract

The present invention relates to a nitride/graphitized carbon nanosheet-coated ternary positive electrode material and a preparation method therefor. The nitride/graphitized carbon nanosheet-coated ternary positive electrode material comprises a ternary positive electrode material base and a coating layer. The coating layer consists of nitride and graphitized carbon. The graphitized carbon is formed in situ in the coating process of the nitride. In the present invention, in the process of coating the nitride on the surface layer of the ternary positive electrode material, a graphitized carbon layer structure is generated in situ. Compared with a physical mixing method, the in-situ generated carbon layer is connected to the base material more tightly, and a conductive network is denser, so that the rate performance of the material is improved to the maximum extent. The ternary positive electrode material has excellent rate performance and cycling stability, the preparation method for the ternary positive electrode material is simple in technological process, and the industrial production can be easily implemented.

Description

氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法Nitride/graphitized carbon nanosheet coated ternary cathode material and preparation method thereof 技术领域technical field
本发明涉及锂电池技术领域，尤其涉及一种氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法。The invention relates to the technical field of lithium batteries, in particular to a nitride/graphitized carbon nanosheet-coated ternary positive electrode material and a preparation method thereof.
背景技术Background technique
锂离子电池作为一种新型的能源储存和转化装置，凭借其工作电压高、能量密度大、库伦效率高、无记忆效应、循环寿命长和对环境影响友好等优点，广泛应用于便携式消费电子设备、新能源汽车和储能电网等领域。锂离子电池的正极材料决定着电池的综合性能，在目前主流正极材料中，三元正极材料LiNi xCo yM 1-x-yO 2(M＝Mn或Al)由于具有较高能量/功率密度和低温性能，因此成为了研究重点。 As a new type of energy storage and conversion device, lithium-ion batteries are widely used in portable consumer electronics devices due to their advantages such as high working voltage, high energy density, high Coulombic efficiency, no memory effect, long cycle life and environmental friendliness. , new energy vehicles and energy storage grids and other fields. The cathode material of a lithium-ion battery determines the comprehensive performance of the battery. Among the current mainstream cathode materials, the ternary cathode material LiNi x Co y M 1-xy O 2 (M=Mn or Al) has higher energy/power density and Low-temperature performance has therefore become a research focus.
随着三元材料中Ni含量的提高，材料容量上升，但其结构稳定性变差，究其原因是Ni-O键键能较弱，晶体结构稳定性变差，尤其是充放电过程中，高活性的界面和电解液发生氧化还原反应，生成非活性岩盐相结构，造成电解液分解，同时释放大量热量，导致电芯胀气、安全性能下降、放电容量衰减以及循环稳定性恶化等一系列问题。目前解决这一问题的主要技术手段之一是进行包覆，包覆剂不仅能够有效避免高活性正极界面和电解液直接接触，缓解副反应发生，而且还能作为快离子导体，为锂离子扩散传输提供良好的通道，进而提升改善倍率性能。目前包覆剂主要有氧化物，如Al 2O 3、TiO 2、ZrO 2、B 2O 3、SiO 2等，尽管该氧化物包覆剂能够改善上述界面稳定性问题，但氧化物大部分属于半导体，电子电导率较低，不能满足大电流充放电要求。相比较氧化物，氮化物 具有更好的耐化学腐蚀性，更加优异的电子电导率和热稳定性，作为包覆剂能够更大限度提升三元材料电性能。 With the increase of Ni content in the ternary material, the capacity of the material increases, but its structural stability becomes poor. The reason is that the Ni-O bond energy is weak and the stability of the crystal structure becomes poor, especially during the charging and discharging process. Oxidation-reduction reactions occur between the highly active interface and the electrolyte to form an inactive rock-salt phase structure, which causes the electrolyte to decompose and release a large amount of heat at the same time, resulting in a series of problems such as cell inflation, safety performance degradation, discharge capacity decay, and cycle stability deterioration. . At present, one of the main technical means to solve this problem is coating. The coating agent can not only effectively avoid the direct contact between the highly active positive electrode interface and the electrolyte, alleviate the occurrence of side reactions, but also act as a fast ion conductor to facilitate the diffusion of lithium ions. The transmission provides a good channel, which in turn improves the magnification performance. At present, the coating agent mainly includes oxides, such as Al 2 O 3 , TiO 2 , ZrO 2 , B 2 O 3 , SiO 2 , etc. Although the oxide coating agent can improve the above interface stability problems, most of the oxides Belonging to semiconductors, the electronic conductivity is low and cannot meet the requirements of high current charging and discharging. Compared with oxides, nitrides have better chemical corrosion resistance, more excellent electronic conductivity and thermal stability, and as coating agents, they can maximize the electrical properties of ternary materials.
目前存在的氮化物包覆技术中，如中国发明专利CN113097459A所公开内容，采用气相沉积包覆方法，该气相反应流程复杂，不易规模化生产。中国发明专利CN112174222A所公开的方法中将待包覆三元正极材料和钛源、含氮化合物进行一步法混合烧结，制备氮化钛包覆三元正极材料，尽管该方法过程简便，便于工业化生产，但在制备过程中，含氮化合物的还原性气体会存在直接与三元材料反应的可能性，从而破坏三元正极主体材料晶格结构，影响材料电性能发挥。Among the currently existing nitride coating technologies, as disclosed in the Chinese invention patent CN113097459A, the gas phase deposition coating method is adopted, and the gas phase reaction process is complicated, and it is not easy to produce on a large scale. In the method disclosed in the Chinese invention patent CN112174222A, the ternary cathode material to be coated, titanium source, and nitrogen-containing compound are mixed and sintered in one step to prepare the titanium nitride-coated ternary cathode material, although the method is simple and convenient for industrial production , but in the preparation process, the reducing gas of the nitrogen-containing compound may directly react with the ternary material, thereby destroying the lattice structure of the ternary positive electrode main material and affecting the electrical performance of the material.
发明内容Contents of the invention
有鉴于此，有必要提供一种氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法，用以解决现有技术中气相沉积包覆法工艺流程复杂，一步法混合烧结法容易破坏三元正极主体材料晶格结构、影响材料性能的技术问题。In view of this, it is necessary to provide a nitride/graphitized carbon nanosheet-coated ternary positive electrode material and its preparation method to solve the complex process of the vapor deposition coating method in the prior art, and the one-step mixed sintering method is easy Technical issues that destroy the lattice structure of the main material of the ternary positive electrode and affect the performance of the material.
本发明的第一方面提供一种氮化物/石墨化碳纳米片包覆三元正极材料，包括三元正极材料基体和包覆层，包覆层由氮化物和石墨化碳组成，且石墨化碳在氮化物的包覆过程中原位形成。A first aspect of the present invention provides a nitride/graphitized carbon nanosheet coated ternary positive electrode material, including a ternary positive electrode material substrate and a coating layer, the coating layer is composed of nitride and graphitized carbon, and graphitized The carbon is formed in situ during the coating of the nitride.
本发明的第二方面提供一种氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，包括以下步骤：A second aspect of the present invention provides a method for preparing a nitride/graphitized carbon nanosheet-coated ternary positive electrode material, comprising the following steps:
提供三元正极材料基体；Provide ternary cathode material matrix;
通过湿法包覆使包覆元素包覆于三元正极材料基体表面获得中间产物；其中，包覆元素为Al、Si、Ti、Zr、Ta、Nb中的一种或多种；Coating the coating element on the surface of the ternary positive electrode material substrate by wet coating to obtain an intermediate product; wherein the coating element is one or more of Al, Si, Ti, Zr, Ta, Nb;
将中间产物与含碳氮化合物混合均匀，经烧结、粉碎、过筛和除铁， 得到氮化物/石墨化碳纳米片包覆三元正极材料。The intermediate product is uniformly mixed with the carbon and nitrogen-containing compound, sintered, pulverized, sieved and iron removed to obtain a nitride/graphitized carbon nanosheet-coated ternary positive electrode material.
与现有技术相比，本发明的有益效果为：Compared with prior art, the beneficial effect of the present invention is:
本发明在三元正极材料表层包覆氮化物的过程中，原位生成了石墨化碳层结构，相比较物理混合的方法，原位生成的碳层与基体材料连接更加紧密，导电网络更加密集，从而最大限度提升材料倍率性能；该三元正极材料具有优异的倍率性能和循环稳定性，其制备方法工艺流程简单，易于实现工业化生产。In the present invention, during the process of coating the nitride on the surface of the ternary positive electrode material, a graphitized carbon layer structure is generated in situ. Compared with the method of physical mixing, the carbon layer generated in situ is more tightly connected to the matrix material, and the conductive network is denser. , so as to maximize the rate performance of the material; the ternary cathode material has excellent rate performance and cycle stability, and its preparation method has a simple process flow and is easy to realize industrial production.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
本发明的第一方面提供一种氮化物/石墨化碳纳米片包覆三元正极材料，包括三元正极材料基体和包覆层，包覆层由氮化物和石墨化碳组成，且石墨化碳在氮化物的包覆过程中原位形成。与无定形碳相比，石墨化碳材料的导电性更好，更有利于提高倍率性能。A first aspect of the present invention provides a nitride/graphitized carbon nanosheet coated ternary positive electrode material, including a ternary positive electrode material substrate and a coating layer, the coating layer is composed of nitride and graphitized carbon, and graphitized The carbon is formed in situ during the coating of the nitride. Compared with amorphous carbon, graphitized carbon materials have better conductivity and are more conducive to improving the rate performance.
本发明中，三元正极材料基体为镍钴锰三元正极材料或镍钴铝三元正极材料中的一种或多种，其结构式为LiNi xCo yM 1-x-yO 2(M＝Mn或Al)。在本发明的一些具体实施方式中，x≥0.8。 In the present invention, the matrix of the ternary positive electrode material is one or more of nickel-cobalt-manganese ternary positive electrode materials or nickel-cobalt-aluminum ternary positive electrode materials, and its structural formula is LiNi x Co y M 1-xy O 2 (M=Mn or Al). In some embodiments of the invention, x > 0.8.
本发明中，氮化物为氮化铝、氮化硅、氮化钛、氮化锆、氮化钽、氮化铌中的一种或多种。In the present invention, the nitride is one or more of aluminum nitride, silicon nitride, titanium nitride, zirconium nitride, tantalum nitride, and niobium nitride.
本发明中，包覆层的厚度为1～100nm。In the present invention, the thickness of the coating layer is 1 to 100 nm.
本发明的第二方面提供一种氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，包括以下步骤：A second aspect of the present invention provides a method for preparing a nitride/graphitized carbon nanosheet-coated ternary positive electrode material, comprising the following steps:
S1、提供三元正极材料基体；S1. Provide ternary cathode material matrix;
S2、通过湿法包覆使包覆元素包覆于三元正极材料基体表面获得中间产物；其中，包覆元素为Al、Si、Ti、Zr、Ta、Nb中的一种或多种；S2. Coating the coating element on the surface of the ternary positive electrode material substrate by wet coating to obtain an intermediate product; wherein the coating element is one or more of Al, Si, Ti, Zr, Ta, Nb;
S3、将中间产物与含碳氮化合物混合均匀，经烧结、粉碎、过筛和除铁，得到氮化物/石墨化碳纳米片包覆三元正极材料。S3, uniformly mixing the intermediate product with the carbon-nitrogen compound, sintering, pulverizing, sieving and removing iron to obtain a nitride/graphitized carbon nanosheet-coated ternary positive electrode material.
本发明通过含碳氮化合物中的氮元素在高温环境中与中间产物表层包覆的过渡金属氧化物反应，生产过渡金属氮化物，同时碳元素在过渡金属的催化石墨化作用下，原位生成石墨化碳纳米片，最终形成了氮化物/石墨化碳纳米片包覆三元正极材料。In the present invention, the transition metal nitride is produced by reacting the nitrogen element in the carbon-nitrogen-containing compound with the transition metal oxide coated on the surface of the intermediate product in a high-temperature environment, and at the same time, the carbon element is generated in situ under the catalytic graphitization of the transition metal Graphitized carbon nanosheets eventually form a nitride/graphitized carbon nanosheets-coated ternary cathode material.
本发明中，提供三元正极材料基体的步骤具体为：将三元正极材料前驱体和锂源混合均匀后经煅烧、粉碎、过筛得到三元正极材料基体。In the present invention, the step of providing the matrix of the ternary positive electrode material is specifically: mixing the precursor of the ternary positive electrode material and the lithium source evenly, and then calcining, pulverizing, and sieving to obtain the matrix of the ternary positive electrode material.
进一步地，三元正极材料前驱体为镍钴锰或镍钴铝的氧化物、氢氧化物、羟基氧化物中的一种或多种；锂源为碳酸锂、氧化锂和氢氧化锂中的一种或几种的混合；三元正极材料前驱体与锂源的摩尔比为1：1～1.15；通过高混机将三元正极材料前驱体和锂源混合均匀；高混机转速为100～1500rpm，进一步为1000rpm，混合处理时间为0.5～5h，进一步为1h；煅烧在氧气气氛下进行，通入氧气气氛的体积浓度≥99％，煅烧温度为500～1200℃，进一步为650～850℃，更进一步为750℃；煅烧时间5～24h，进一步为10～14h，更进一步为12h。Further, the precursor of the ternary positive electrode material is one or more of oxides, hydroxides, and oxyhydroxides of nickel-cobalt-manganese or nickel-cobalt-aluminum; the lithium source is lithium carbonate, lithium oxide, and lithium hydroxide. One or several kinds of mixture; the molar ratio of the precursor of the ternary cathode material to the lithium source is 1:1~1.15; the precursor of the ternary cathode material and the lithium source are mixed evenly by the high mixer; the speed of the high mixer is 100 ～1500rpm, further 1000rpm, the mixing treatment time is 0.5～5h, further 1h; the calcination is carried out under the oxygen atmosphere, the volume concentration of the oxygen atmosphere is ≥99%, the calcination temperature is 500～1200℃, further 650～850 °C, further 750 °C; calcination time 5-24h, further 10-14h, further 12h.
进一步地，三元正极材料基体的制备过程中，还加入掺杂剂以提高正极材料的结构稳定性。例如，掺杂剂可以为二氧化锆、三氧化铝、二氧化钛、氧化镁等，本发明对此不作限制。更进一步地，掺杂剂与三元正极材料前驱体的摩尔比0.0001～0.1：1。Furthermore, during the preparation of the matrix of the ternary cathode material, dopants are also added to improve the structural stability of the cathode material. For example, the dopant can be zirconium dioxide, aluminum trioxide, titanium dioxide, magnesium oxide, etc., which is not limited in the present invention. Furthermore, the molar ratio of the dopant to the precursor of the ternary cathode material is 0.0001˜0.1:1.
本发明中，包覆元素与三元正极材料基体的质量比为0.0001～0.005：1，进一步为0.0004～0.003:1，更进一步为0.0008～0.001:1。In the present invention, the mass ratio of the coating element to the matrix of the ternary positive electrode material is 0.0001-0.005:1, further 0.0004-0.003:1, and further 0.0008-0.001:1.
本发明中，湿法包覆的步骤具体为：In the present invention, the steps of wet coating are specifically:
将三元正极材料基体加入到第一溶剂中，形成溶液Ⅰ；adding the ternary cathode material matrix to the first solvent to form solution I;
将含包覆元素的化合物加入到第二溶剂中，形成溶液Ⅱ；adding the compound containing the capping element to the second solvent to form solution II;
将溶液Ⅱ缓慢加入到溶液Ⅰ中，保温反应，经固液分离、烘干获得中间产物。Slowly add solution II to solution I, keep warm for reaction, and obtain intermediate product through solid-liquid separation and drying.
进一步地，含包覆元素的化合物为含包覆元素的醇盐。在本发明的一些具体实施方式中，含包覆元素的化合物为三乙醇铝、正硅酸乙酯、钛酸四丁酯、异丙醇钛、异丙醇锆、五乙氧基钽、五乙氧基铌中的一种或多种；第一溶剂和第二溶剂为水、甲醇、乙醇、异丙醇、乙二醇中的一种或多种。Furthermore, the compound containing a coating element is an alkoxide containing a coating element. In some specific embodiments of the present invention, the compound containing coating elements is aluminum triethoxide, ethyl orthosilicate, tetrabutyl titanate, titanium isopropoxide, zirconium isopropoxide, tantalum pentaethoxide, pentaethoxide One or more of niobium ethoxide; the first solvent and the second solvent are one or more of water, methanol, ethanol, isopropanol, and ethylene glycol.
进一步地，溶液Ⅰ中，三元正极材料基体与溶剂的用量比为1～20g：100ml，进一步为10～20g：100ml；溶液Ⅱ中，含包覆元素的化合物与溶剂的用量比为0.01～10g：100ml，进一步为0.04～1g：100ml，更进一步为0.1～0.6g：100ml，更进一步为0.2g：100ml。Further, in solution I, the dosage ratio of the ternary cathode material matrix to the solvent is 1-20g: 100ml, further 10-20g: 100ml; in solution II, the dosage ratio of the compound containing the coating element to the solvent is 0.01- 10g: 100ml, further 0.04-1g: 100ml, further 0.1-0.6g: 100ml, further 0.2g: 100ml.
进一步地，保温反应的温度为30～80℃，进一步为60℃，保温反应的时间0.5～5h，进一步为1～2h；烘干的温度为80～120℃，烘干的时间5～20h。Further, the temperature of the heat preservation reaction is 30-80°C, further 60°C, the time of the heat preservation reaction is 0.5-5h, further 1-2h; the temperature of the drying is 80-120°C, and the drying time is 5-20h.
本发明中，含碳氮化合物为氨基酸、三聚氰胺、尿素中的一种或多种。进一步地，含碳氮化合物与中间产物的质量比为5～20：100，若质量比过高会导致表层包覆层(氮化物和石墨化碳)过多，影响材料容量发挥；过低则包覆层少，达不到包覆的效果；进一步为6～17：100，更进一步为10：100；通过高混机将含碳氮化合物与中间产物混合均匀，高混机转速为1000～4000rpm，进一步为2000rpm，混合处理时间为1～8h，进一步为2h；烧结在惰性气体(如氩气或氮气等)的保护下进行，烧结温度为500～1000℃，进一步为800℃，烧结时间3～12h，进一步为6h。In the present invention, the carbon-nitrogen-containing compound is one or more of amino acids, melamine, and urea. Further, the mass ratio of carbon and nitrogen-containing compounds to intermediate products is 5-20:100. If the mass ratio is too high, it will cause too much surface coating (nitride and graphitized carbon), which will affect the capacity of the material; if it is too low, the There are few coating layers, and the coating effect cannot be achieved; the further ratio is 6-17:100, and the further ratio is 10:100; the carbon-nitrogen-containing compound and the intermediate product are mixed evenly by a high-speed mixer, and the speed of the high-speed mixer is 1000~ 4000rpm, further 2000rpm, mixing treatment time is 1-8h, further 2h; sintering is carried out under the protection of inert gas (such as argon or nitrogen, etc.), the sintering temperature is 500-1000°C, further 800°C, the sintering time 3~12h, further 6h.
实施例1Example 1
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni 0.83Co 0.12Mn 0.05(OH) 2、240g氢氧化锂(LiOH·H 2O)和1.5g纳米二氧化锆(ZrO 2)，转移进高混机中混合，转速1000rpm，混合时间1h后取出，随后将其转移到马弗炉中煅烧，氧气气氛下750℃烧结12h，烧结结束后取出物料，随后进行粉碎和过筛后获得三元正极材料基体； (1) Weigh 500g nickel cobalt manganese hydroxide ternary cathode material precursor Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 , 240g lithium hydroxide (LiOH·H 2 O) and 1.5g nano zirconium dioxide (ZrO 2 ), transferred to a high mixer and mixed at a speed of 1000rpm, taken out after mixing for 1h, then transferred to a muffle furnace for calcination, and sintered at 750°C for 12h under an oxygen atmosphere. After sintering, the material was taken out, and then crushed and sieved Finally, the matrix of the ternary cathode material is obtained;
(2)称取400g三元正极材料基体，转移至3000ml乙醇溶剂中，形成溶液Ⅰ；称取2g异丙醇钛包覆剂转移至1000ml乙醇溶剂中，形成溶液Ⅱ；分别搅拌10min后，将溶液Ⅱ缓慢加入到溶液Ⅰ中，持续进行搅拌，水浴加热至60℃，保温1h，混合溶液进行压滤，固液分离后得到滤饼，随后将其转移至100℃烘箱内部进行烘干，保温10h，获得烘干后的中间产物；(2) Weigh 400g of ternary cathode material matrix, transfer it to 3000ml ethanol solvent to form solution I; weigh 2g titanium isopropoxide coating agent and transfer it to 1000ml ethanol solvent to form solution II; after stirring for 10min respectively, Slowly add solution II to solution I, continue to stir, heat in a water bath to 60°C, keep warm for 1 hour, press filter the mixed solution, and obtain a filter cake after solid-liquid separation, then transfer it to an oven at 100°C for drying, keep warm 10h, obtain the intermediate product after drying;
(3)称取300g中间产物和30g三聚氰胺，进行混合后，转入至高混机中高速搅拌，2000rpm转速下搅拌2h，随后转入氩气气氛马弗炉中，氩气气氛下800℃烧结6h，烧结完成后，将所得物料进行粉碎、过筛和除铁，即为最终氮化物/石墨化碳纳米片包覆三元正极材料。(3) Weigh 300g of the intermediate product and 30g of melamine, mix them, transfer them to a high-speed mixer, stir at a speed of 2000rpm for 2h, then transfer them to an argon atmosphere muffle furnace, and sinter at 800°C for 6h under an argon atmosphere After the sintering is completed, the obtained material is crushed, sieved and iron-removed, which is the final nitride/graphitized carbon nanosheet-coated ternary cathode material.
扣式电池测试：将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi 0.83Co 0.12Mn 0.05)、乙炔黑、PVDF按照94:4:4的比例混合，以NMP为溶剂混合均匀后涂覆在铝箔上，制作成2032扣式电池进行电化学性能测试，测试电压范围2.8～4.3V，首周按照0.1C/0.1C充放电，接下来1C/1C循环测试50周。最终测试结果：0.1C放电容量210mAh/g，1C放电容量199mAh/g，50周循环容量保持率98.6％。 Button battery test: Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ~ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity 210mAh/g, 1C discharge capacity 199mAh/g, 50-cycle cycle capacity retention rate 98.6%.
实施例2Example 2
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni 0.83Co 0.12Mn 0.05(OH) 2、240g氢氧化锂(LiOH·H 2O)和1.5g纳米二氧化 锆(ZrO 2)，转移进高混机中混合，转速1000rpm，混合时间1h后取出，随后将其转移到马弗炉中煅烧，氧气气氛下750℃烧结12h，烧结结束后取出物料，随后进行粉碎和过筛后获得三元正极材料基体； (1) Weigh 500g nickel cobalt manganese hydroxide ternary cathode material precursor Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 , 240g lithium hydroxide (LiOH·H 2 O) and 1.5g nano zirconium dioxide (ZrO 2 ), transferred to a high mixer and mixed at a speed of 1000rpm, taken out after mixing for 1h, then transferred to a muffle furnace for calcination, and sintered at 750°C for 12h under an oxygen atmosphere. After sintering, the material was taken out, and then crushed and sieved Finally, the matrix of the ternary cathode material is obtained;
(2)称取400g三元正极材料基体，转移至3000ml乙醇溶剂中，形成溶液Ⅰ；称取0.4g异丙醇钛包覆剂转移至1000ml乙醇溶剂中，形成溶液Ⅱ；分别搅拌10min后，将溶液Ⅱ缓慢加入到溶液Ⅰ中，持续进行搅拌，水浴加热至60℃，保温1h，混合溶液进行压滤，固液分离后得到滤饼，随后将其转移至100℃烘箱内部进行烘干，保温10h，获得烘干后的中间产物；(2) Weigh 400g of ternary cathode material matrix, transfer it to 3000ml ethanol solvent to form solution I; weigh 0.4g titanium isopropoxide coating agent and transfer it to 1000ml ethanol solvent to form solution II; after stirring for 10min respectively, Slowly add solution II to solution I, continue to stir, heat in a water bath to 60°C, keep it warm for 1 hour, press filter the mixed solution, and obtain a filter cake after solid-liquid separation, and then transfer it to an oven at 100°C for drying. Insulated for 10 hours to obtain the dried intermediate product;
(3)称取300g中间产物、15g三聚氰胺，进行混合后，转入至高混机中高速搅拌，2000rpm转速下搅拌2h，随后转入氩气气氛马弗炉中，氩气气氛下800℃烧结6h，烧结完成后，将所得物料进行粉碎、过筛和除铁，即为最终氮化物/石墨化碳纳米片包覆三元正极材料。(3) Weigh 300g of the intermediate product and 15g of melamine, mix them, transfer them to a high-speed mixer, stir at a speed of 2000rpm for 2 hours, then transfer them to an argon atmosphere muffle furnace, and sinter at 800°C for 6 hours under an argon atmosphere After the sintering is completed, the obtained material is crushed, sieved and iron-removed, which is the final nitride/graphitized carbon nanosheet-coated ternary cathode material.
扣式电池测试：将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi 0.83Co 0.12Mn 0.05)、乙炔黑、PVDF按照94:4:4的比例混合，以NMP为溶剂混合均匀后涂覆在铝箔上，制作成2032扣式电池进行电化学性能测试，测试电压范围2.8～4.3V，首周按照0.1C/0.1C充放电，接下来1C/1C循环测试50周。最终测试结果：0.1C放电容量208mAh/g，1C放电容量194mAh/g，50周循环容量保持率93.7％。 Button battery test: Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ~ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity of 208mAh/g, 1C discharge capacity of 194mAh/g, 50-cycle cycle capacity retention rate of 93.7%.
实施例3Example 3
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni 0.83Co 0.12Mn 0.05(OH) 2、240g氢氧化锂(LiOH·H 2O)和1.5g纳米二氧化锆(ZrO 2)，转移进高混机中混合，转速1000rpm，混合时间1h后取出，随后将其转移到马弗炉中煅烧，氧气气氛下750℃烧结12h，烧结结束后取出物料，随后进行粉碎和过筛后获得三元正极材料基体； (1) Weigh 500g nickel cobalt manganese hydroxide ternary cathode material precursor Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 , 240g lithium hydroxide (LiOH·H 2 O) and 1.5g nano zirconium dioxide (ZrO 2 ), transferred to a high mixer and mixed at a speed of 1000rpm, taken out after mixing for 1h, then transferred to a muffle furnace for calcination, and sintered at 750°C for 12h under an oxygen atmosphere. After sintering, the material was taken out, and then crushed and sieved Finally, the matrix of the ternary cathode material is obtained;
(2)称取400g三元正极材料基体，转移至3000ml乙醇溶剂中，形成溶液Ⅰ；称取1g异丙醇钛包覆剂转移至1000ml乙醇溶剂中，形成溶液Ⅱ；分别搅拌10min后，将溶液Ⅱ缓慢加入到溶液Ⅰ中，持续进行搅拌，水浴加热至60℃，保温2h，混合溶液进行压滤，固液分离后得到滤饼，随后将其转移至100℃烘箱内部进行烘干，保温10h，获得烘干后的中间产物；(2) Weigh 400g of ternary cathode material matrix, transfer it to 3000ml ethanol solvent to form solution I; weigh 1g of titanium isopropoxide coating agent and transfer it to 1000ml ethanol solvent to form solution II; after stirring for 10min respectively, Slowly add solution II to solution I, continue to stir, heat to 60°C in a water bath, keep warm for 2 hours, press filter the mixed solution, and obtain a filter cake after solid-liquid separation, then transfer it to an oven at 100°C for drying, keep warm 10h, obtain the intermediate product after drying;
(3)称取300g中间产物和20g三聚氰胺，进行混合后，转入至高混机中高速搅拌，2000rpm转速下搅拌2h，随后转入氩气气氛马弗炉中，氩气气氛下800℃烧结6h，烧结完成后，将所得物料进行粉碎、过筛和除铁，即为最终氮化物/石墨化碳纳米片包覆三元正极材料。(3) Weigh 300g of the intermediate product and 20g of melamine, mix them, transfer them to a high-speed mixer, stir at a speed of 2000rpm for 2h, then transfer them to an argon atmosphere muffle furnace, and sinter at 800°C for 6h under an argon atmosphere After the sintering is completed, the obtained material is crushed, sieved and iron-removed, which is the final nitride/graphitized carbon nanosheet-coated ternary cathode material.
扣式电池测试：将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi 0.83Co 0.12Mn 0.05)、乙炔黑、PVDF按照94:4:4的比例混合，以NMP为溶剂混合均匀后涂覆在铝箔上，制作成2032扣式电池进行电化学性能测试，测试电压范围2.8～4.3V，首周按照0.1C/0.1C充放电，接下来1C/1C循环测试50周。最终测试结果：0.1C放电容量209mAh/g，1C放电容量196mAh/g，50周循环容量保持率97.9％。 Button battery test: Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ~ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity 209mAh/g, 1C discharge capacity 196mAh/g, 50-cycle cycle capacity retention rate 97.9%.
实施例4Example 4
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni 0.83Co 0.12Mn 0.05(OH) 2、240g氢氧化锂(LiOH·H 2O)和1.5g纳米二氧化锆(ZrO 2)，转移进高混机中混合，转速1000rpm，混合时间1h后取出，随后将其转移到马弗炉中煅烧，氧气气氛下750℃烧结12h，烧结结束后取出物料，随后进行粉碎和过筛后获得三元正极材料基体； (1) Weigh 500g nickel cobalt manganese hydroxide ternary cathode material precursor Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 , 240g lithium hydroxide (LiOH·H 2 O) and 1.5g nano zirconium dioxide (ZrO 2 ), transferred to a high mixer and mixed at a speed of 1000rpm, taken out after mixing for 1h, then transferred to a muffle furnace for calcination, and sintered at 750°C for 12h under an oxygen atmosphere. After sintering, the material was taken out, and then crushed and sieved Finally, the matrix of the ternary cathode material is obtained;
(2)称取400g三元正极材料基体，转移至3000ml乙醇溶剂中，形成溶液Ⅰ；称取6g异丙醇钛包覆剂转移至1000ml乙醇溶剂中，形成溶液Ⅱ；分别搅拌10min后，将溶液Ⅱ缓慢加入到溶液Ⅰ中，持续进行搅拌，水 浴加热至60℃，保温2h，混合溶液进行压滤，固液分离后得到滤饼，随后将其转移至100℃烘箱内部进行烘干，保温10h，获得烘干后的中间产物；(2) Weigh 400g of ternary cathode material matrix, transfer it to 3000ml ethanol solvent to form solution I; weigh 6g titanium isopropoxide coating agent and transfer it to 1000ml ethanol solvent to form solution II; after stirring for 10min respectively, Slowly add solution II to solution I, continue to stir, heat to 60°C in a water bath, keep warm for 2 hours, press filter the mixed solution, and obtain a filter cake after solid-liquid separation, then transfer it to an oven at 100°C for drying, keep warm 10h, obtain the intermediate product after drying;
(3)称取300g中间产物、50g三聚氰胺，进行混合后，转入至高混机中高速搅拌，2000rpm转速下搅拌2h，随后转入氩气气氛马弗炉中，氩气气氛下800℃烧结6h，烧结完成后，将所得物料进行粉碎、过筛和除铁，即为最终氮化物/石墨化碳纳米片包覆三元正极材料。(3) Weigh 300g of the intermediate product and 50g of melamine, mix them, transfer them to a high-speed mixer, stir at a speed of 2000rpm for 2 hours, then transfer them to an argon atmosphere muffle furnace, and sinter at 800°C for 6 hours under an argon atmosphere After the sintering is completed, the obtained material is crushed, sieved and iron-removed, which is the final nitride/graphitized carbon nanosheet-coated ternary cathode material.
扣式电池测试：将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi 0.83Co 0.12Mn 0.05)、乙炔黑、PVDF按照94:4:4的比例混合，以NMP为溶剂混合均匀后涂覆在铝箔上，制作成2032扣式电池进行电化学性能测试，测试电压范围2.8～4.3V，首周按照0.1C/0.1C充放电，接下来1C/1C循环测试50周。最终测试结果：0.1C放电容量207mAh/g，1C放电容量193mAh/g，50周循环容量保持率97.4％。 Button battery test: Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ~ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity 207mAh/g, 1C discharge capacity 193mAh/g, 50-cycle cycle capacity retention rate 97.4%.
实施例5Example 5
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni 0.83Co 0.12Mn 0.05(OH) 2、240g氢氧化锂(LiOH·H 2O)和1.5g纳米二氧化锆(ZrO 2)，转移进高混机中混合，转速1000rpm，混合时间1h后取出，随后将其转移到马弗炉中煅烧，氧气气氛下750℃烧结12h，烧结结束后取出物料，随后进行粉碎和过筛后获得三元正极材料基体； (1) Weigh 500g nickel cobalt manganese hydroxide ternary cathode material precursor Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 , 240g lithium hydroxide (LiOH·H 2 O) and 1.5g nano zirconium dioxide (ZrO 2 ), transferred to a high mixer and mixed at a speed of 1000rpm, taken out after mixing for 1h, then transferred to a muffle furnace for calcination, and sintered at 750°C for 12h under an oxygen atmosphere. After sintering, the material was taken out, and then crushed and sieved Finally, the matrix of the ternary cathode material is obtained;
(2)称取400g三元正极材料基体，转移至3000ml乙醇溶剂中，形成溶液Ⅰ；称取10g异丙醇钛包覆剂转移至1000ml乙醇溶剂中，形成溶液Ⅱ；分别搅拌10min后，将溶液Ⅱ缓慢加入到溶液Ⅰ中，持续进行搅拌，水浴加热至60℃，保温2h，混合溶液进行压滤，固液分离后得到滤饼，随后将其转移至100℃烘箱内部进行烘干，保温10h，获得烘干后的中间产物；(2) Weigh 400g of ternary cathode material matrix, transfer it to 3000ml ethanol solvent to form solution I; weigh 10g titanium isopropoxide coating agent and transfer it to 1000ml ethanol solvent to form solution II; after stirring for 10min respectively, Slowly add solution II to solution I, continue to stir, heat to 60°C in a water bath, keep warm for 2 hours, press filter the mixed solution, and obtain a filter cake after solid-liquid separation, then transfer it to an oven at 100°C for drying, keep warm 10h, obtain the intermediate product after drying;
(3)称取300g中间产物和60g三聚氰胺，进行混合后，转入至高混机中高速搅拌，2000rpm转速下搅拌2h，随后转入氩气气氛马弗炉中，氩气气氛下800℃烧结6h，烧结完成后，将所得物料进行粉碎、过筛和除铁，即为最终氮化物/石墨化碳纳米片包覆三元正极材料。(3) Weigh 300g of the intermediate product and 60g of melamine, mix them, transfer them to a high-speed mixer, stir at a speed of 2000rpm for 2h, then transfer them to an argon atmosphere muffle furnace, and sinter at 800°C for 6h under an argon atmosphere After the sintering is completed, the obtained material is crushed, sieved and iron-removed, which is the final nitride/graphitized carbon nanosheet-coated ternary cathode material.
扣式电池测试：将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi 0.83Co 0.12Mn 0.05)、乙炔黑、PVDF按照94:4:4的比例混合，以NMP为溶剂混合均匀后涂覆在铝箔上，制作成2032扣式电池进行电化学性能测试，测试电压范围2.8～4.3V，首周按照0.1C/0.1C充放电，接下来1C/1C循环测试50周。最终测试结果：0.1C放电容量198mAh/g，1C放电容量176mAh/g，50周循环容量保持率97.5％。 Button battery test: Mix the obtained nitride/graphitized carbon nanosheet-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, and use NMP as a solvent to mix Evenly coated on aluminum foil, made into 2032 button battery for electrochemical performance test, the test voltage range is 2.8 ~ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity of 198mAh/g, 1C discharge capacity of 176mAh/g, 50-cycle cycle capacity retention rate of 97.5%.
对比例1Comparative example 1
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni 0.83Co 0.12Mn 0.05(OH) 2、240g氢氧化锂(LiOH·H 2O)和1.5g纳米二氧化锆(ZrO 2)，转移进高混机中混合，转速1000rpm，混合时间1h后取出，随后将其转移到马弗炉中煅烧，氧气气氛下750℃烧结12h，烧结结束后取出物料，随后进行粉碎和过筛后获得三元正极材料基体； (1) Weigh 500g nickel cobalt manganese hydroxide ternary cathode material precursor Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 , 240g lithium hydroxide (LiOH·H 2 O) and 1.5g nano zirconium dioxide (ZrO 2 ), transferred to a high mixer and mixed at a speed of 1000rpm, taken out after mixing for 1h, then transferred to a muffle furnace for calcination, and sintered at 750°C for 12h under an oxygen atmosphere. After sintering, the material was taken out, and then crushed and sieved Finally, the matrix of the ternary cathode material is obtained;
(2)称取400g三元正极材料基体，转移至3000ml乙醇溶剂中，形成溶液Ⅰ；称取2g异丙醇钛包覆剂转移至1000ml乙醇溶剂中，形成溶液Ⅱ；分别搅拌10min后，将溶液Ⅱ缓慢加入到溶液Ⅰ中，持续进行搅拌，水浴加热至60℃，保温1h，混合溶液进行压滤，固液分离后得到滤饼，随后将其转移至100℃烘箱内部进行烘干，保温10h，获得烘干后的中间产物；(2) Weigh 400g of ternary cathode material matrix, transfer it to 3000ml ethanol solvent to form solution I; weigh 2g titanium isopropoxide coating agent and transfer it to 1000ml ethanol solvent to form solution II; after stirring for 10min respectively, Slowly add solution II to solution I, continue to stir, heat in a water bath to 60°C, keep warm for 1 hour, press filter the mixed solution, and obtain a filter cake after solid-liquid separation, then transfer it to an oven at 100°C for drying, keep warm 10h, obtain the intermediate product after drying;
(3)称取300g中间产物和30g三聚氰胺，进行混合后，转入至高混机中高速搅拌，2000rpm转速下搅拌2h，随后转入氧气气氛马弗炉中，氧气气氛下800℃烧结6h，烧结完成后，将所得物料进行粉碎、过筛和 除铁，即为最终氮化物包覆三元正极材料。(3) Weigh 300g of the intermediate product and 30g of melamine, mix them, transfer them to a high-speed mixer, stir at 2000rpm for 2h, then transfer them to an oxygen atmosphere muffle furnace, and sinter at 800°C for 6h under an oxygen atmosphere. After completion, the obtained material is crushed, sieved and iron removed, which is the final nitride-coated ternary cathode material.
扣式电池测试：将得到的氮化物包覆三元正极材料(LiNi 0.83Co 0.12Mn 0.05)、乙炔黑、PVDF按照94:4:4的比例混合，以NMP为溶剂混合均匀后涂覆在铝箔上，制作成2032扣式电池进行电化学性能测试，测试电压范围2.8～4.3V，首周按照0.1C/0.1C充放电，接下来1C/1C循环测试50周。最终测试结果：0.1C放电容量206mAh/g，1C放电容量190mAh/g，50周循环容量保持率97.0％。 Button battery test: Mix the obtained nitride-coated ternary cathode material (LiNi 0.83 Co 0.12 Mn 0.05 ), acetylene black, and PVDF in a ratio of 94:4:4, mix evenly with NMP as a solvent, and coat on an aluminum foil Firstly, make 2032 button cells for electrochemical performance test, the test voltage range is 2.8 ~ 4.3V, charge and discharge according to 0.1C/0.1C in the first week, and then 1C/1C cycle test for 50 weeks. Final test results: 0.1C discharge capacity 206mAh/g, 1C discharge capacity 190mAh/g, 50-cycle cycle capacity retention rate 97.0%.
与现有技术相比，本发明的有益效果为：Compared with prior art, the beneficial effect of the present invention is:
(1)制备方法工艺流程简单，纯固相反应过程，条件便于控制，易于规模化工业生产；(1) The preparation method has a simple technological process, a pure solid phase reaction process, convenient control of conditions, and easy large-scale industrial production;
(2)整个包覆过程分为湿法预包覆和后续高温氮化步骤，相比较一次包覆过程，预包覆过程不仅为后续氮化提供了前驱体，而且还能保护三元正极基体材料免遭后续含碳氮还原性气体破坏；(2) The entire coating process is divided into wet pre-coating and subsequent high-temperature nitriding steps. Compared with the one-time coating process, the pre-coating process not only provides a precursor for subsequent nitriding, but also protects the ternary cathode substrate The material is protected from subsequent carbon and nitrogen-containing reducing gas damage;
(3)石墨化纳米片在过渡金属催化作用下直接原位生成，相比较物理混合方法，材料之间接触更紧密，导电碳层网络分布更加均匀，从而大幅提升复合材料导电性，较大限度增强三元正极材料倍率性能；(3) Graphitized nanosheets are directly generated in situ under the catalysis of transition metals. Compared with the physical mixing method, the contact between the materials is closer, and the distribution of the conductive carbon layer network is more uniform, thereby greatly improving the conductivity of the composite material and maximizing Enhance the rate performance of ternary cathode materials;
(4)氮化物生成的同时，伴随着石墨化碳包覆层的形成，既增强了离子电导率又增强的电子电导率。(4) At the same time as the formation of nitrides, accompanied by the formation of graphitized carbon coating, both ionic conductivity and electronic conductivity are enhanced.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed in the present invention can easily think of changes or Replacement should be covered within the protection scope of the present invention.

Claims (10)

  1. 一种氮化物/石墨化碳纳米片包覆三元正极材料，其特征在于，包括三元正极材料基体和包覆层，包覆层由氮化物和石墨化碳组成，且石墨化碳在氮化物的包覆过程中原位形成。A nitride/graphitized carbon nanosheet coated ternary positive electrode material is characterized in that it includes a ternary positive electrode material substrate and a coating layer, the coating layer is composed of nitride and graphitized carbon, and the graphitized carbon is in nitrogen Formed in situ during the coating process of the compound.
  2. 根据权利要求1所述氮化物/石墨化碳纳米片包覆三元正极材料，其特征在于，所述氮化物为氮化铝、氮化硅、氮化钛、氮化锆、氮化钽、氮化铌中的一种或多种；所述包覆层的厚度为1～100nm。The nitride/graphitized carbon nanosheet-coated ternary positive electrode material according to claim 1, wherein the nitride is aluminum nitride, silicon nitride, titanium nitride, zirconium nitride, tantalum nitride, One or more types of niobium nitride; the thickness of the cladding layer is 1-100nm.
  3. 一种如权利要求1～2中任一项所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，其特征在于，包括以下步骤：A method for preparing a nitride/graphitized carbon nanosheet-coated ternary positive electrode material according to any one of claims 1 to 2, characterized in that it comprises the following steps:
    提供三元正极材料基体；Provide ternary cathode material matrix;
    通过湿法包覆使包覆元素包覆于三元正极材料基体表面获得中间产物；其中，所述包覆元素为Al、Si、Ti、Zr、Ta、Nb中的一种或多种；Coating the coating element on the surface of the ternary positive electrode material substrate by wet coating to obtain an intermediate product; wherein the coating element is one or more of Al, Si, Ti, Zr, Ta, Nb;
    将所述中间产物与含碳氮化合物混合均匀，经烧结、粉碎、过筛和除铁，得到氮化物/石墨化碳纳米片包覆三元正极材料；其中，烧结的气氛为惰性气体。The intermediate product is uniformly mixed with carbon and nitrogen-containing compounds, sintered, pulverized, sieved and iron removed to obtain a nitride/graphitized carbon nanosheet-coated ternary positive electrode material; wherein the sintering atmosphere is an inert gas.
  4. 根据权利要求3所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，其特征在于，所述包覆元素与三元正极材料基体的质量比为0.0001～0.005：1。The method for preparing a nitride/graphitized carbon nanosheet-coated ternary positive electrode material according to claim 3, wherein the mass ratio of the coating element to the matrix of the ternary positive electrode material is 0.0001-0.005:1.
  5. 根据权利要求3所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，其特征在于，所述湿法包覆的步骤具体为：According to the preparation method of the nitride/graphitized carbon nanosheet-coated ternary positive electrode material according to claim 3, it is characterized in that the step of wet coating is specifically:
    将三元正极材料基体加入到第一溶剂中，形成溶液Ⅰ；adding the ternary cathode material matrix to the first solvent to form solution I;
    将含包覆元素的化合物加入到第二溶剂中，形成溶液Ⅱ；adding the compound containing the capping element to the second solvent to form solution II;
    将所述溶液Ⅱ缓慢加入到所述溶液Ⅰ中，保温反应，经固液分离、烘干获得中间产物。Slowly add the solution II into the solution I, keep warm for reaction, and obtain an intermediate product through solid-liquid separation and drying.
  6. 根据权利要求5所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，其特征在于，所述含包覆元素的化合物为含包覆元素的醇盐； 所述第一溶剂和第二溶剂为水、甲醇、乙醇、异丙醇、乙二醇中的一种或多种。According to the preparation method of the nitride/graphitized carbon nanosheet coated ternary positive electrode material according to claim 5, it is characterized in that, the compound containing the coating element is an alkoxide containing the coating element; the first solvent And the second solvent is one or more of water, methanol, ethanol, isopropanol, and ethylene glycol.
  7. 根据权利要求5所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，其特征在于，所述保温反应的温度为30～80℃，保温反应的时间0.5～5h。The method for preparing a nitride/graphitized carbon nanosheet-coated ternary positive electrode material according to claim 5, wherein the temperature of the heat preservation reaction is 30-80° C., and the time of the heat preservation reaction is 0.5-5 hours.
  8. 根据权利要求3所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，其特征在于，所述含碳氮化合物为氨基酸、三聚氰胺、尿素中的一种或多种。The method for preparing a nitride/graphitized carbon nanosheet-coated ternary cathode material according to claim 3, wherein the carbon-nitrogen-containing compound is one or more of amino acids, melamine, and urea.
  9. 根据权利要求3所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，其特征在于，所述含碳氮化合物与中间产物的质量比为5～20：100。The method for preparing a nitride/graphitized carbon nanosheet-coated ternary positive electrode material according to claim 3, wherein the mass ratio of the carbon-nitrogen-containing compound to the intermediate product is 5-20:100.
  10. 根据权利要求3所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法，其特征在于，所述烧结温度为500～1000℃，烧结时间3～12h。The method for preparing a nitride/graphitized carbon nanosheet-coated ternary positive electrode material according to claim 3, wherein the sintering temperature is 500-1000° C., and the sintering time is 3-12 hours.
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